Wholly aromatic liquid crystalline polymers containing sulfonated ionic monomer units and laminates thereof

ABSTRACT

A melt processable wholly aromatic liquid crystalline polymer capable of forming an anisotropic melt phase at a temperature below approximately 400 DEG  C. having enhanced adhesion properties containing from approximately 0.05 to approximately 2.0 mole percent of a recurring sulfonated, ionic moiety in the backbone of the polymer. The polymer is useful for the production of laminate structures.

FIELD OF INVENTION

The present invention relates to a wholly aromatic liquid crystallinepolymer containing the residue of a sulfonated ionic monomer unit in thepolymer backbone. The polymer exhibits enhanced adhesion properties andis useful for forming laminate materials.

BACKGROUND ART

Due to their availability and characteristics, wholly aromatic liquidcrystalline polymers are desirably used in the formation of laminatearticles. However, the use of these polymers therefor has been hinderedby their poor adhesion properties to other laminate forming materials.The adhesion of glass, ceramic, polymeric and metallic layers to whollyaromatic liquid crystalline polymers has required the application ofbinders, heat and compression to the interfacial surfaces of the layers.

SUMMARY OF THE INVENTION

It has now been discovered that the addition of a small amount of awholly aromatic ionic moiety to the backbone of wholly aromatic liquidcrystalline polymers will improve the adhesion properties of theresulting polymers. The ionic moiety useful in the present invention istypically the residue of a wholly aromatic monomer having a metallicsulfonate group pendent thereto. The ionic moiety may be included in thebackbone of wholly aromatic polyesters aliphatic-aromatic polyesters,polycarbonates, poly(ester-carbonates), poly(ester-amides) andpolyaramides to provide polymers exhibiting enhanced adhesionproperties.

In accordance with the present invention there is described meltprocessable wholly aromatic liquid crystalline polymers capable offorming anisotropic melt phases at temperatures below approximately 400°C. having enhanced adhesion properties containing a small amount ofrecurring moieties of a sulfonated, ionic moiety into the backbone ofthe polymer.

The wholly aromatic liquid crystalline polymers of the present inventionare useful for forming laminates which may include layers of ceramics,glasses, metals, other polymers and mixtures thereof. The inventionfinds particular use in the formation of laminate structures containinglayers of metals and other polymers adhered to layers of the liquidcrystalline polymers wherein an intermediate application of an adhesivematerial is undesirable.

DETAILED DESCRIPTION OF THE INVENTION

It has now been discovered that the incorporation of a small amount ofrecurring moieties of a sulfonated, wholly aromatic, ionic moiety in thebackbone of a melt processable liquid crystalline polymer will improvethe adhesion characteristics of the polymer. Typically, theincorporation of approximately 0.05 to approximately 2.0 mole percent ofat least one ionic moiety of the formulae: ##STR1## wherein M⁺ is acation, in the backbone of a melt processable wholly aromatic polymerselected from the group consisting of wholly aromatic polyesters,aliphatic-aromatic polyesters, polycarbonates, poly(ester-carbonates),poly(ester-amides) and polyaramides will enhance the adhesion propertiesof the polymer. The cations useful in the ionic moiety are typicallymetals selected from the group consisting of sodium, potassium, lithium,zinc, calcium, cadmium, magnesium, barium and mixtures thereof. Thelinkage of the ionic moiety in the liquid crystalline polymer backbonemay occur at the 1,3- or 1,4- positions of the ionic moiety unit withrespect to the sulfonate group at the 5-position. Additionalrepresentative ionic moieties of this invention may be produced bysubstituting the sulfonates described hereinbefore onto ester-formingnuclei derived from hydroquinone, hydroxynaphthoic acids, hydroxybenzoicacids, substituted hydroxybenzoic acids, cycloaliphatic dicarboxylicacids, etc.

Metals found to adhere particularly well to these polymers are selectedfrom copper, silver, gold, tin, platinum, nickel, aluminum and alloysthereof. A variety of liquid crystalline, as well as tractable andintractable polymers, will readily adhere to the novel ionic moietycontaining polymers described herein. When forming a laminate structurecontaining a plurality of liquid crystalline polymer layers, theincorporation of a small amount of recurring moieties of the ionic unitin the backbone of each polymer will provide excellent adhesionproperties. Useful polymer layers of the present invention may include,but are not limited to, polyalkylene terephthalate, (e.g., polybutyleneterephthalate and polyethylene terephthalate), polybenzimidazoles,polybenzimidazolones, polybenzoxazoles, polybenzthiozoles, nylons,polyvinylchlorides, wholly aromatic polyesters, polyarylates,polyamides, polyaramides, polyimides, poly(amide-imides),poly(ester-carbonates), poly(ester-amides) and the like.

The appropriate cation of the ionic moiety is dependent upon thematerial to be adhered to the liquid crystal polymer. If the desiredmaterial is a metal, the cation of the ionic moiety is typicallyselected from alkali metals, e.g., sodium, potassium and lithium.However, if the material is a polymer, the cation of the ionic moiety istypically selected from zinc, calcium, cadmium, magnesium and barium.When adhering metals to the melt processable wholly aromatic liquidcrystalline polymers of the present invention, a preferred ionic moietyis of the formula: ##STR2## also known as 5-sodiosulfoisophthaloyl. Whenadhering polymer substrates to the liquid crystalline ionomer of thepresent invention, a preferred ionic monomer is of the formula: ##STR3##also known as 5-zincsulfoisophthaloyl.

One liquid crystal polymer of the present invention having enhancedadhesion properties and useful for forming laminate structures is a meltprocessable wholly aromatic liquid crystalline polyester capable offorming an anisotropic melt phase at a temperature of below about 350°C. containing recurring moieties of from approximately 10 toapproximately 90 mole percent of 4-oxybenzoyl, from approximately 90 toapproximately 10 mole percent of 6-oxy-2-naphthoyl, (the subject matterof U.S. Pat. No. 4,161,470 herein incorporated by reference in itsentirety) and from approximately 0.05 to approximately 2.0 mole percentof the sulfonated, ionic moiety described hereinbefore. Typically, thepolymer will contain recurring moieties of from approximately 65 toapproximately 85 mole percent of 4-oxybenzoyl, e.g., approximately 75mole percent, from approximately 15 to approximately 35 mole percent of6-oxy-2-naphthoyl, e.g., approximately 25 mole percent, and fromapproximately 0.10 to approximately 1.75 mole percent of the sulfonatedionic moiety, e.g., approximately 1.0 mole percent, and exhibit ananisotropic melt processing temperature of below about 325° C.Preferably, however, the polymer will contain recurring moieties ofapproximately 73 mole percent of 4-oxybenzoyl, approximately 27 molepercent of 6-oxy-2-naphthoyl and approximately 1.0 mole percent of thesulfonated ionic moiety, e.g., 5-sodiosulfoisophthaloyl or5-zincsulfoisophthaloyl and exhibit a melt processing temperature ofbelow about 300° C.

Another polymer of the present invention is a polyester capable offorming an anisotropic melt phase at a temperature below about 400° C.,containing recurring moieties of from approximately 3 to approximately10 mole percent of 6-oxy-2-naphthoyl, approximately 20 to approximately70 mole percent of 4-oxybenzoyl, approximately 7.5 to approximately 38.5mole percent of terephthoyl, approximately 7.5 to approximately 38.5mole percent of 4,4'-dioxydiphenyl moiety (the subject matter of U.S.Pat. No. 4,473,682 herein incorporated by reference in its entirety) andapproximately 0.05 to approximately 2.0 mole percent of at least one ofthe sulfonated, ionic moieties described hereinbefore. Still anothermelt processable wholly aromatic polyester of the invention capable offorming an anisotropic melt phase at a temperature below about 320° C.contains recurring moieties of from approximately 20 to approximately 40mole percent of 6-oxy-2-naphthoyl, approximately 10 to approximately 50mole percent of 4-oxybenzoyl, approximately 5 to approximately 30 molepercent of the residue of hydroquinone, approximately 5 to approximately30 mole percent of terephthoyl, (the subject matter of U.S. Pat. No.4,219,461 herein incorporated by reference in its entirety) andapproximately 0.05 to approximately 2.0 mole percent of the sulfonated,ionic moiety described hereinbefore. Yet another polymer of theinvention is a copolyester capable of forming an anisotropic melt phaseat a temperature below about 340° C., containing recurring moieties offrom approximately 33.3 mole percent of p-hydroxybenzoyl, approximately33.3 mole percent of residue of hydroquinone, approximately 33.3 molepercent of isophthaloyl, (the subject matter of U.S. Pat. No. 3,637,595herein incorporated by reference in its entirety), and approximately0.05 to about 2.0 mole percent of the sulfonated, ionic moiety describedhereinbefore.

The laminate structures of the present invention are generallyconstructed of at least first and second layers although a laminatecontaining multiple layers, i.e., three or more layers, is contemplatedby the invention. The first layer is generally formed of the novel ionicmonomer containing polymer described herein, and the second or thirdlayer is formed of a glass, ceramic, metallic, polymeric component ormixtures thereof. Typically, the structure can contain alternatinglayers of the polymers of the present invention when three or morelayers are included in the laminate. While the application of a bindingagent to the interfacial surfaces of the layers followed by heating andcompressing will promote adhesion, the laminate can be formed bycompressing the layers at an elevated temperature for sufficient time topromote adhesion without the use of a binding agent.

These wholly aromatic liquid crystalline polymers will commonly exhibitweight average molecular weights of approximately 2,000 to 220,000, andpreferably approximately 10,000 to 75,000, e.g. approximately 20,000 to50,000. Such molecular weights are generally measured by end groupdetermination via infrared spectroscopy on compression molded films.Alternatively, light scattering techniques on polymers dissolved in aone to one volume concentration ofhexafluoroisopropanol-pentafluorophenol (HFIP-PFP) solution ma beemployed to determine the molecular weight.

The ionic unit containing polymers of the present invention may beformed by a variety of techniques whereby organic monomer compoundspossessing functional groups which upon condensation form the requisiterecurring moieties are reacted. Typical methods of forming liquidcrystalline polymers of the present invention are described U.S. Pat.Nos. 3,316,326; 3,890,256; 4,067,852; 4,219,461; 4,473,682; and5,015,722 herein incorporated by reference in their entirety.

The polymers described herein may be considered crystalline in the sensethat fibers melt extruded therefrom exhibit X-ray diffraction patternsusing Ni-filtered CuKα radiation and flat plate cameras characteristicof polymeric crystalline materials. In spite of the crystallinitycommonly observed, the wholly aromatic polymers of the present inventionnevertheless may be easily melt processed in all instances.

The resulting polymer inherent viscosities (I.V.) were determined in a1:1 V/V HFIP-PFP solution of 0.1 percent by weight concentration at 60°C. according to the following equation:

    I.V.=1n(ηrel)/c

where c concentration of solution (0.1 percent by weight), and ηrel=relative viscosity. The relative viscosity was measured by dividingthe flow time in a capillary viscometer of the polymer solution by theflow time for the pure solvent. The polymer was subject to differentialscanning calorimetry (DSC) at a 20° C./min heating rate to determinemelt point temperature.

When forming fibers and films of the present invention, the extrusionorifice may be selected from among those commonly utilized during themelt extrusion of such shaped articles. For instance, the shapedextrusion orifice may be in the form of a rectangular slit (i.e., a slitdie) when forming a polymeric film. When forming a filamentary material,the spinneret selected may contain one and preferably a plurality ofextrusion orifices. For instance, a standard conical spinneretcontaining 1 to 2000 holes (e.g., 6 to 1500 holes) such as commonly usedin the melt spinning of polyethylene terephthalate, having a diameter ofapproximately 1 to 70 mils (e.g., 5 to 40 mils) may be utilized. Yarnsof approximately 20 to 200 continuous filaments are commonly formed. Themelt-spinnable polyester is supplied to the extrusion orifice at atemperature above its melting point (e.g., at a temperature of about300° to 380° C), and at a temperature of about 335° to 375° C. in apreferred embodiment. The polyester of the present invention exhibits ahighly attractive balance between its melting and heat deflectiontemperatures (HDT). The heat deflection temperature will varyingdependent upon the actual composition of the polymer, particularly,6-hydroxy-2-naphthoic acid content. It also depends on whether thepolymer contains glass or other mineral fillers known in the art.Filling with glass will sometimes cause an increase in HDT for somematerials, and little if any for others. The heat deflection temperatureof a molded article may be determined in accordance with the procedureof ASTM D648 wherein the deflection temperature under load at 264 psi isascertained.

Subsequent to extrusion through the shaped orifice the resultingfilamentary material or film is passed in the direction of its lengththrough a solidification or quench zone wherein the molten filamentarymaterial or film is transformed to a solid filamentary material or film.The resulting fibers commonly have denier per filament of approximately1 to 50, and preferably a denier per filament of approximately 1 to 20.

The as-spun fibers of this invention may be subjected to heat treatmentin an oven while relaxed or under mild restraint to provided highstrength fibers useful for a variety of industrial applications such asplastic, rubber reinforcement, etc. In the heat-treating process, fibersamples, as skeins or on bobbins are usually heated in an oven having aninert atmosphere that is continuously purged by flow of inert gasthrough the oven to remove by-products from the vicinity of the fiber.Temperatures approaching the fusion point, but sufficiently below toprevent interfilament fusion, are employed. Preferably, maximumtemperature is reached in a stepwise fashion. Thermal treatment timecommonly ranges from a few minutes to several days. As the fiber isthermally treated, its melting temperature is increased.

Tenacity (breaking tenacity), elongation (breaking elongation), andinitial modulus were obtained by breaking a single filament (Datareported are averages of 10 breaks). Single filaments were broken with agauge length (distance between jaws) of 2.5 cm. (1.0 inch). The resultson 3 or more filaments are averaged. All samples were elongated at aconstant rate of extension (20% elongation/minute for fibers having anelongation of under 8%) until the samples broke. The tenacity(grams/denier), elongation (percent) and initial modulus (grams/denier)as described in ASTM D3822 were obtained from the load-elongation curveand the measured denier.

The following examples are presented as illustrations of the claimedinvention. It should be understood, however, that the invention is notlimited to the specific details set forth in the examples.

EXAMPLE 1

To a 2 liter 3-neck "slim Jim" flask equipped with a Vigreaux column andcondenser, nitrogen inlet, thermocouple and C-shaped 316 stainless steelstirrer were charged 4-hydroxybenzoic acid (4.38 moles),6-hydroxy-2-naphthoic acid (1.62 moles), and 5-sodiosulfoisophthalicacid, sodium salt (0.06 moles or 1.0%). Since 5-sodiosulfoisophthalicacid, sodium salt can function as an esterification catalyst noadditional catalyst was necessary. The flask was immersed in a sand bathand provided with means to accurately control the temperature, andthoroughly purged of oxygen by evacuating and flushing with nitrogenthree times before the addition of acetic anhydride (2.5% molar excess).The flask was then placed in a fluidized sand bath and heated accordingto a preprogrammed, time-temperature cycle while purging the contents ofthe flask with nitrogen as follows: to a temperature of 125° C. over aperiod of 50 minutes; to 140° C. over 40 minutes; to 150° C over 20minutes; to 200° C. over 45 minutes; to 210° C. over 5 minutes; to 220°C. over 6 minutes; to 335° C. over 115 minutes; and to 340° C. over 10minutes. The time-temperature profile was designed to allow adequatetime for acetylation of the monomers followed by oligomerization andfinally polymerization. As the temperature of the flask increased,acetic acid began to distill over and was collected in a graduatedcylinder. The flask was slowly evacuated (in 100 mbar increments). Thereading of the torque indicator was noted at the beginning of thisvacuum period. Under vacuum at 340° C. the viscosity of the reactantsgradually increased indicating polymerization. When the increase intorque reached a predetermined level ( Δ torque≈50 mV), the vacuum wasreleased (nitrogen was purged into the system). The Vigreaux column andcondenser, nitrogen inlet, thermocouple and stirrer were removed fromthe flask and the formed polymer was allowed to cool. Finally, the flaskwas broken and the polymer plug removed. The plug was cut into severalpieces and ground into small particles. Upon characterization, thepolymer exhibited an inherent viscosity, as measured in one to oneconcentration of 1:1 V/V HFIP-PFP, of 6.2 dl/g and a melting temperatureof 264° C. measured by DSC.

EXAMPLES 2 through 5

Procedures similar to Example 1 were performed to produce polymerscontaining 0 mole %, 0.5 mole % and 2.0 mole % of the5-sodiosulfoisophthaloyl unit. The polymer was melt extruded into acontinuous filament of about 5 denier per filament. More specifically,the polymer melt while at a temperature of about 320° C. was extrudedthrough a spinneret provided with a single hole jet having a diameter of0.127 mm and a length of 0.178 mm. The extruded filament was quenched inambient air (i.e., at 72° F. and 65 percent relatively humidity). Theas-spun filament was taken up at a rate of 800 meters per minute.

The resulting as-spun wholly aromatic polyester fibers exhibited theaverage single filament properties after thermal treatment in a drynitrogen flow at 300° C. for 8 hours as reported below:

    ______________________________________                                        Fiber Containing 0 mole percent of 5-Sodiosulfoisophthaloyl                   Unit                                                                          Melting Point:        286° C.                                          Melt Viscosity @ 300° C.:                                                                    526 @ 10.sup.3 sec.sup.-1                               Inherent Viscosity:   7 dl/gm                                                 As-Spun Tenacity:     11 gm/d                                                 As-Spun Elongation:   2.5%                                                    As-Spun Modulus:      520 gm/d                                                Heat-Treated Tenacity:                                                                              28 gm/d                                                 Heat-Treated Elongation:                                                                            5%                                                      Heat-Treated Modulus: 530 gm/d                                                Fiber Containing 0.5 mole percent of 5-                                       Sodiosulfoisophthaloyl Unit                                                   Melting Point:        269° C.                                          Melt Viscosity @ 300° C.:                                                                    801 @ 10.sup.3 sec.sup.-1                               Inherent Viscosity:   6.2 dl/gm                                               As-Spun Tenacity:     6.1 gm/d                                                As-Spun Elongation:   1.5%                                                    As-Spun Modulus:      464 gm/d                                                Heat-Treated Tenacity:                                                                              11 gm/d                                                 Heat-Treated Elongation:                                                                            2.4%                                                    Heat-Treated Modulus: 590 gm/d                                                Fiber Containing 1.0 mole percent of 5-                                       Sodiosulfoisophthaloyl Unit                                                   Melting Point:        264° C.                                          Melt Viscosity @ 300° C.:                                                                    778 @ 10.sup.3 sec.sup.-1                               Inherent Viscosity:   6.19 dl/gm                                              As-Spun Tenacity:     5.5 gm/d                                                As-Spun Elongation:   1.4%                                                    As-Spun Modulus:      471 gm/d                                                Heat-Treated Tenacity:                                                                              7.1 gm/d                                                Heat-Treated Elongation:                                                                            1.8%                                                    Heat-Treated Modulus: 415 gm/d                                                Fiber Containing 2.0 mole percent of 5-                                       Sodiosulfoisophthaloyl Unit                                                   Melting Point:        265° C.                                          Melt Viscosity @ 300° C.:                                                                    898 @ 10.sup.3 sec.sup.-1                               Inherent Viscosity:   *                                                       As-Spun Tenacity:     *                                                       As-Spun Elongation:   *                                                       As-Spun Modulus:      *                                                       Heat-Treated Tenacity:                                                                              *                                                       Heat-Treated Elongation:                                                                            *                                                       Heat-Treated Modulus: *                                                       ______________________________________                                         *no data, material could not be spun                                     

EXAMPLES 6 and 7

As a measure of the adhesive strength of the polyesters with and withoutthe 5-sodiosulfoisophthaloyl unit, films were produced from polyestercompositions of Formulation #1 and Formulation #2 as follows:

Formulation #1: 4-hydroxybenzoic acid (4.38 moles) and6-hydroxy-2-naphthoic acid (1.62 moles); and

Formulation #2: 4-hydroxybenzoic acid (4.38 moles),6-hydroxy-2-naphthoic acid (1.62 moles), and 5-sodiosulfoisophthalicacid, sodium salt (0.06 moles or 1.0 wt. %).

Films of Formulations #1 (containing no sulfonated, ionic unit) and #2(containing 1.0 wt. % of sulfonated, ionic unit) were individuallysandwiched between 0.0625 inch aluminum foil and Kapton film sheets, anda 0.0625 inch sheet of anodized aluminum alloy was placed onto theKapton sheet. Kapton film was placed between the polymer film and theanodized aluminum alloy sheet to initiate adhesive failure. Thelaminates were compression molded at 295° C. and 25 psi for 25 minutes.

Adhesion strengths, i.e., roller peel strengths, were determined by thefloating roller peel strength method, ASTM D3167-76(1986). Two samples,5 inch wide specimens were tested from each composite; peel strengthswere averaged over a 3 inch length. Results of adhesion tests of severalof the samples are presented below for comparison:

    ______________________________________                                        Sample        Peel Strength, lb/in                                            ______________________________________                                        Formulation #1                                                                              3.75                                                            Formulation #1                                                                              3.12                                                            Formulation #2                                                                              11.50                                                           Formulation #2                                                                              9.57                                                            ______________________________________                                    

The polyesters of Formulation #2 containing the sodiosulfoisophthaloylunit, showed significantly enhanced adhesion to aluminum foil over thepolyesters of Formulation #1 containing no ionic unit.

EXAMPLES 8 through 20

According to the procedure utilized in Example 1, additional whollyaromatic liquid crystalline polymers containing 5-sodiosulfoisophthaloyl(SSI) units were produced. The formulations contained 4-hydroxybenzoicacid (HBA), 6-hydroxy-2-naphthoic acid (HNA), terephthalic acid (TA),isophthalic acid (IA), hydroquinone (HQ), paraaminobenzoic acid (PABA),4,4 '-dihydroxydiphenyl (BP), N-acetyl-p-aminophenol (AA),2,6-dihydroxynaphthalene (DHN) and SSI. Rheological properties weremeasured by DSC at 20° C/min. heating rate for each of Formulations3-15.

Formulation #3 contained a reaction mixture of:

60 mole % HBA,

5 mole % HNA,

16.5 mole % TA,

17.5 mole % BP, and

1 mole % SSI

The resulting polymer had an inherent viscosity (IV) of 4.67 dl/g, andmelt viscosities (MVs) of 1500 poise at a shear rate of 10² sec⁻¹ and539 poise at a shear rate of 10³ sec⁻¹ measured at 345° C. The polymerexhibited a crystallization temperature (T_(c)) of 241.4° C.

Formulation #4, comparative example of Formulation #3, containedidentical quantities of reactants but no SSI monomer.

Formulation #4 contained a reaction mixture of:

60 mole % HBA,

5 mole % HNA,

17.5 mole % TA,

17.5 mole % BP, and

0 mole % SSI

The resulting polymer has an IV of to 7.5 dl/g, and MVs of 900 poise ata shear rate of 10² sec.⁻¹ and 350 poise at a shear rate of 10³ sec⁻¹measured at 345° C. The polymer exhibited a melt endotherm peak (T_(m))of to 347° C., and a T_(c) of 295° C.

Formulation #5 contained a reaction mixture of:

60 mole % HBA,

5 mole % HNA,

17 mole % IA,

17.5 mole % HQ, and

0.5 mole % SSI

The resulting polymer had an (IV) of 1.17 dl/g, and an MVs of 2214 poiseat a shear rate of 10² and sec⁻¹ and 841 poise at a shear rate of 10⁻³sec.⁻¹ measured at 300° C. The polymer exhibited a glass transitiontemperature (T_(g)) of 125.4° C.

Formulation #6 contained a reaction mixture of:

60 mole % HBA,

5 mole % HNA,

16.5 mole % IA,

17.5 mole % HQ, and

1 mole % SSI

The resulting polymer had an IV of 1.45 dl/g, and MVs of 985 poise at ashear rate of 10² sec⁻¹ and 523 poise at a shear rate of 10³ sec⁻¹measured at 340° C. The polymer exhibited T_(g) of 125.3° C.

Formulation #7 contained a reaction mixture of:

72 mole % HBA,

27 mole % HNA,

0.5 mole % HQ, and

0.5 mole % SSI

The resulting polymer had an IV of 6.99 dl/g, and MVs of 4005 poise at ashear rate of 10² sec.⁻¹ and 1096 poise at a shear rate of 10³ sec⁻¹measured at 300° C. The polymer exhibited a T_(m) of 267.6° C. and aT_(c) of 219.9° C.

Formulation #8 contained a reaction mixture of:

72 mole % HBA,

26 mole % HNA,

1 mole % HQ, and

1 mole % SSI

The resulting polymer has an IV of 5.80 dl/g, and MVs of 2360 poise at ashear rate of 10² sec⁻¹ and 710 poise at a shear rate of 10³ sec⁻¹measured at 300° C. The polymer exhibited a T_(m) of 270.9° C. and aT_(c) of 221.2° C.

Formulation #9 contained a reaction mixture of:

72 mole % HBA,

27 mole % HNA,

0.5 mole % HQ, and

0.5 mole % SSI

The resulting polymer had an IV of 5.86 dl/g, and MVs of 3147 poise at ashear rate of 10² sec⁻¹ and 900 poise at a shear rate of 10³ sec⁻¹measured at 300° C. The polymer exhibited a T_(m) of 265.1° C. and aT_(c) of 218.5° C.

Formulation #10 contained a reaction mixture of:

72 mole % HBA,

26 mole % HNA,

1 mole % HQ, and

1 mole % SSI

The resulting polymer has an IV of 5.41 dl/g, and MVs of 2237 posie at ashear rate of 10² sec⁻¹ and 669 poise at a shear rate of 10³ sec⁻¹measured at 300° C. The polymer exhibited a T_(m) of 270.6° C. and aT_(c) of 221.7° C.

Formulation #11 contained a reaction mixture of:

72 mole % HBA,

26 mole % HNA,

1 mole % AA, and

1 mole % SSI

The resulting polymer had an IV of 5.30 dl/g, and MVs of 2186 poise at ashear rate of 10² sec⁻¹ and 684 poise at a shear rate of 10³ sec⁻¹measured at 300° C. The polymer exhibited a T_(m) of 267.6° C. and aT_(c) of 218.4° C.

Formulation #12 contained a reaction mixture of:

72 mole % HBA,

26 mole % HNA,

1 mole % AA, and

1 mole % SSI

The resulting polymer has an IV of 5.05 dl/g, and MVs of 1940 poise at ashear rate of 10, sec⁻¹ and 625 poise at a shear rate of 10³ sec⁻¹measured at 300° C. The polymer exhibited a T_(m) of 269.7° C. and aT_(c) of 221.1° C.

Formulation #13 contained a reaction mixture of:

72 mole % HBA,

26 mole % HNA,

1 mole % PABA, and

1 mole % SSI

The resulting polymer had an IV of 6.66 dl/g, and MVs of 3194 poise at ashear rate of 10² sec⁻¹ and 980 poise at a shear rate of 10³ sec⁻¹measured at 300° C. The polymer exhibited a T_(m) of 275.5° C. and aT_(c) of 224.9° C.

Formulation #14 contained a reaction mixture of:

72 mole % HBA,

26 mole % HNA,

1 mole % DHN, and

1 mole % SSI

The resulting polymer has an IV of 4.49 dl/g, and MVs of 948 poise at ashear rate of 10² sec⁻¹ and 381 poise at a shear rate of 10³ sec⁻¹measured at 300° C. The polymer exhibited a T_(m) of 267.7° C. and aT_(c) of 220.1° C.

Formulation #15 contained a reaction mixture of:

72 mole % HBA,

26 mole % HNA,

1 mole % DHN, and

1 mole % SSI

The resulting polymer had an IV of 4.95 dl/g, and MVs of 1437 poise at ashear rate of 10² sec⁻¹ and 514 poise at a shear rate of 10³ sec⁻¹measured at 300° C. The polymer exhibited a T_(m) of 267.4° C. and aT_(c) of 219.7° C.

We claim:
 1. A melt processable wholly aromatic liquid crystallinepolymer capable of forming an anisotropic melt phase at a temperaturebelow about 400° C. which exhibits improved adhesion to glass, metallic,ceramic, and polymeric substrates, consisting of from approximately 0.05to approximately 2.0 mole percent of at least one recurring ionic moietyselected from the formulae: ##STR4## in the polymer backbone, wherein M⁺is a cation and the polymer is selected from the group consisting ofwholly aromatic polyesters, poly(ester-carbonates), poly(esteramides)and polyaramides, and wherein the wholly aromatic polyester consists ofrecurring units of 6-hydroxy-2-naphthoyl and 4-hydroxybenzoyl.
 2. Theliquid crystalline polymer according to claim 1 wherein the cation isselected from the group consisting of sodium, lithium, potassium, zinc,calcium, cadmium, magnesium, barium and mixtures thereof.
 3. The liquidcrystalline polymer according to claim 2 wherein the ionic moiety is ofthe formula: ##STR5##
 4. The liquid crystalline polymer according toclaim 3 wherein the concentration of the ionic moiety is approximately0.5 mole percent.
 5. The liquid crystalline polymer according to claim 2wherein the ionic moiety is of the formula: ##STR6##
 6. A meltprocessable liquid crystalline polyester capable of forming ananisotropic melt phase at a temperature below about 375° C. whichexhibits improved adhesion to glass, metallic, ceramic, and polymericsubstrates, consisting of recurring moieties of (a) from approximately10 to approximately 90 mole percent of 4-oxybenzoyl; (b) fromapproximately 90 to approximately 10 mole percent of 6-oxy-2-naphthoyl;and (c) from approximately 0.05 to approximately 2.0 mole percent of atleast one recurring ionic moiety selected from the formulae: ##STR7##wherein M⁺ is a cation.
 7. The polymer according to claim 6 wherein thecation is selected from the group consisting of sodium, lithium,potassium, zinc, calcium, cadmium, magnesium, barium and mixturesthereof.
 8. The polymer according to claim 7 wherein the concentrationof the ionic moiety is approximately 1.0 mole percent.
 9. The polymeraccording to claim 6 wherein the ionic moiety is of the formula:##STR8##
 10. The polymer according to claim 9 which exhibits enhancedadhesion to metal, ceramic, glass and polymeric materials.